Method of controlling insects with heterocyclic norbornene derivatives



United States Patent "Ice 3,281,317 METHOD OF CONTROLLING INSECTS WITHHETEROCYCLIC NORBORNENE DERIVATIVES Victor Mark, Olivette, Mo., assignorto Monsanto Company, a corporation of Delaware No Drawing. Originalapplication Nov. 13, 1962, Ser.

No. 237,338. Divided and this application June 25,

1965, Ser. No. 482,314

4 Claims. (Cl. 167-33) This application is a division of Serial Number237,- 338, filed November 13, 1962.

This invention relates to novel structures and procedures for theirpreparation. More specifically, the invention relates to pesticides,especially insecticides, having unusual and interesting propertiesprepared by the halogenation of Diels-Allder adducts of alkylatedhalocyclopentadiene and a cyclic olefin.

Diels-Alder adducts of hexachlorocyclopentadienes are known to be toxicnot only to insects but also to domestic animals, desirable wild lifeand to humans. By the substitution of organic radicals, especially alkyl groups, on the allylic carbon atoms of thehexachlorocyclopentadiene molecule, reduction in toxicity of the adductsto the warm blooded animals occurs without serious reduction inmicrobiological activity. This advantageous reduction of the toxicityhazards is the fundamental objective of this invention, and thismodification of the spectrum of activity is a significant step in thedevelopment of biological toxicants.

In application Serial No. 132,570, filed August 21, 1961, there aredescribed and claimed Diels-Alder adduction procedures and novelcompounds prepared by these methods. Certain of these adducts are usedin the practice of this invention whereby new compounds with increasedactivity are prepared. Specifically, the new procedure involves thehalogenation of the adducts to form compounds which cannot be preparedby the adduction of the diene with dienophiles having the desiredhalogen substit-uents.

The new biological toxicants have the structure WQ ai/EX wherein X isselected from the class consisting of chlorine and bromine; wherein R isselected firom the class consisting of hydrocarbon radicals of the groupconsisting of alkyl having up to 12 carbon atoms, alkenyl having up to12 carbon atoms, alkynyl having up to 12 carbon atoms, and cycloalkylradicals having :from three to seven carbon atoms; and the saidhydrocarbon radicals having substituents of the class consisting ofalkyloxy, alkylthio, chlorine, bromine and phenyl, the alkyl moiety ofsaid substituents having up to four carbon atoms; wherein Y is selectedfrom the class consisting of R, Z and hydrogen; wherein Z is selectedfrom the group consist-ing of X and hydrogen; and wherein W is selectedfrom the class consisting of oxygen and sulfur.

3,28 l ,3 l 7 Patented Oct. 25, 1 966 1,2,3 ,4 tetrachloro-5 ,5 -diethylcy-clopentadiene 1,2,3 ,4,5-pentachloro-5-n-decylcyclopentadiene 1,2,3,4,5-pentachloro-4-dodecynylcyclopentadiene1,2,3,4-tetrabromo-5-cyc1ohexycyclopentadiene5-benzyl-5-bromo-1,2,3,4-tetrachlorocyclopentadiene 5(Zm-butyl-thiopropyl) -1,2,3 ,4,5-pentachlorocyclopentadiene 5(2ethylhexyl)-1,2,3 ,4-tet-rabromocyclopentadiene 5,5-dibenzyl-1,2,3,4-tetracholo cyclopentadiene In accordance with this invention it hasbeen found that the new active compounds, which cannot be advantageouslyprepared by direct adduction of the halocyclopentadiene with thehalodihydrofuran or the halodihydrothiopene, can be made by thehalogenation of adducts of the halocyclopentadiene and eitherdihydrofuran or dihydrothiophene. In accordance with the invention, tosaid adducts are treated with chlorine or bromine under specificconditions where-by the new class of compounds are formed.

At temperatures of from C. to 300 C. or higher the replacement ofhydrogen by the halogen with evolution of hydrogen chloride can beaccomplished. It is, however, possible to carry out the reaction at muchlower temperatures in the presence of a suitable catalyst, which iscapable of activating the halogen. The best catalysts are those whichcause a homolytic activation of the halogen molecule, tor exampleactinic irradiation, ultraviolet light, X-rays and gamma rays. Peroxidecatalysts, such as benzoylperoxide, di-t-butyl peroxide andtbutylperbenzoate are also useful. By simple irradiation of thereactants with light, and especially ultraviolet light, the reactionbetween the halogen and the Diels-Alder adduct will even take place ator below room temperatures, but optimum conditions usually involvetemperatures between 50 C. and 150 C. The reaction will also proceed inthe presence of peroxide catalysts under conditions which induce theformation of free radicals. The activation of the halogen may also beeffected by means of catalysts of the Lewis acid type, such as AlCl FeClBF and AlBr In general, any condition or combination of conditions whichinduce the evolution of hydrogen halide are suitable.

Further details of the process for preparing the new compounds are settorth in the following examples.

Example 1 A 23.6 gram sample of a Diels-Alder adduct of 1,2,3,4,5-pentachloro-5-ethylcyclopentadiene and dihydrofuran was dissolved in350 ml. of carbon tetrachloride and charged to a flask containing asuitable gas inlet tube. Gaseous chlorine was introduced whileirradiating the mixture with an ultraviolet lamp until 10.9 grams ofchlorine had been absorbed. The reaction mixture was maintained duringthis operation at a temperature of 30 to 50 C. The product was recoveredby evaporating 3 4 the carbon tetrachloride and was found to haveanindex presence of benzoyl peroxide produced a compound of of refraction,n 1.5498 and the structure the structure H C1 H 01 a H 01H: Cl 5 l H 0c1 I s I 01 0 01 I 01 I H H 0 01 Cl H m H 1 Example 6 This Compound Wasf d to be very active in the con- The Diels-Alder adduct ofdihyd'rofuran and 1,2,3,4,5- trol of mosquito larvae; 0.16 part permillion provided pentach-loro-5-isopropylcyclopentadiene was producedand a 100% kill and 0.078 part per million provided a 90% dissolved in150 ml. of carbon tetrachloride. Five grams kill. of chlorine wereintroduced while irradiating the reac- ExampleZ tion vessel with brightultraviolet light. The product recovered in 78% yield n =l.5628) wasfound to have The preceding example was repeated except that the theStructure adduct of dihydrofuran and l,2,3,4,5-pentachlor05-meth- 20 H01 ylcyclopentadiene was used in place of S-ethyl deriva- C1 tive. Theresulting product (M.P. 100-102 C.) was produced in a 97% yield. It wasfound by spectra and Cl elemental analysis to have the structure I C1 0H 01 Example 7 I 01 0 01 I The procedure of Example 6 was repeatedexcept that H the cyclopentadinene was replaced by 1,2,3,4,S-pentabr0-C1 C1 mo-S-methylcyclopentadiene and dihydrofuran by dihydrothiop'hene.The product had the structure This compound was found to be very good inthe con- H 01 trol of mosquito larvae, 100% kill being efiected by H301: H 0.078 part per million whereas 0.039 part per million Br provided a80% kill. Br 3 Example 3 40 B! I The procedure of Example 1 was repeatedexcept using Br v the adduct of1,2,3,4,5-pentachloro-5-(2ethylhexyl)cyclo- H 01 pentadiene anddihydrofuran. The product, n 1.5390 Example 8 was found to have thestructure The procedure of Example 2 was repeated except that CHa thel,2,3,4,5-pentabromo-5 rnethylcyclopentadiene was H used in place of the1,2,3,4,5-pentachlor0-5-methylcycl0 H C] pentadiene. The compoundproduced had the structure cmomomomiJn-CH; 01

H H 01 01 H O Br H I O1 0 Br I H CH! 0 H 01 Example 4 Example 9 Theprocess of Example 1 was repeated using the adduct Of dihydrofuran and1,2,3,4-tetrachloro-5,5-dirnethyl- 0 The procedure of Example 4 wasrepeated except that fiyclopentadiene- The P "D 15578 Was foundapproximately half of the amount of chlorine was used. to have thestructure A compound separated from the reaction mixture with thestructure H 01 v i H 0H 01 H C a H 0 01 I I 01 H CH i 1 a H H Example 5Example 10 The bromination of the adduct of l,2,3,4-tetrachloro- A nadduct of dihydrothiophene and 1,2,3,4-tetrachloro-5,5-dimethylcyclopentadiene and dihydrothiophene in the5-(3-meth0xypropyl)cyclopentadiene is treated with one molar proportionof bromine to form a compound of the structure:

Example 11 H C1 Cl-GHz-CH 01H 1 tax H 01 Example 12 The procedure ofExample 1 was repeated except that the adduct of5,5-diethyl-1,2,3,4,-tetrachlorocyclopentadiene was used in place of the-m0noet'hyl analog. The resultant product had n 1.5582 and the structureH 01 H50: Ci H K sCn C1 Since the new compounds are useful asinsecticides, bactericides, nematocides and herbicides, they may beformulated as required for the intended use. Compositions of the activecomponent and various adjuvants may be used in various physical forms,for example solutions, dispersions or as pulverulent formulations. Theymay be prepared as concentrates for dilution prior to use, or as dilutedispersions or solutions for immediate use. The preparation of aqueousformulations may take place ust prior to use by dispersing in theavailable water to the extent desired. Since concentrated dispersionsmay exceed the water solubility of the active component, it 1sfrequently desirable to avoid local excesses of active components byproviding agents which assure the complete and uniform dispersion of theformulation components. Suitable agents are the surface active agents,which may be cationic, anionic, nonionic or those which possess bothcationic and anionic properties.

The surfactants may contain both hydrophilic and hydrophobic functions,and thereby are in part attracted to water and still have waterrepellant properties. The oilsoluble components are attracted by onefunction which is water repellant and in this manner, localconcentrations of the formulation components are avoided. Examplesacids, resin soaps such as salts of abietic acid, sulfuric acid salts ofhigh molecular weight organic compounds, algin soaps, ethylene oxidecondensated with fatty acid, alkyl phenols and mercaptans, and othersimple and polymeric compositions having bothhydrophilic and hydrophobicfunctions so as to enable the mixing of otherwise immiscibleingredients. Other examples are described in detail in the textbookSurface Active Agents and Detergents, Schwartz, Perry and Berch(Interscience Publishers Inc., New York, 1958).

The above-described surfactants are particularly useful in aqueousformulations which have a heterogeneous component that must bemaintained in dispersed condition. The heterogeneous component may be awater-immiscible organic solvent which will aid in the dissolution ofthe water-insoluble excess of active component or other extraneous orcollateral component of the formulation. The organic solvent may bepresent in the amount of 0.05 to to 10 percent by weight of the finalformulation, depending upon the quantity of undissolved substancespresent. The conventional liquid formulation will usually have from 0.5to 2 percent of the organic solvent. Suitable organic solvents for theactive components are the organic alcohols, ketones and hydrocarbons,for example isopropanol, benzene, acetone, methyl ethyl ketone,kerosene, and chlorinated hydrocarbons. The proportions of such organicliquid additives will depend upon the solubility properties of theactive ingredient and may require as little as 1 percent or as much as20 percent in order to provide a uniform distribution within theformulation, which is capable of maintaining its distributed stateduring storage, use and after application to the soil or plant surfaces.

Aqueous formulations may contain solid substances when the formulationis prepared 'by adding a wettable dust to water. In order to suspend thelarger quantity of water insoluble solids more of the surfactant isusually required, for example 1.0 to 10 percent. The solid component ofthe wettable powders, in addition to providing a carrier for theconcentrates, will serve as an indicator in the final formulations topermit the visual estimation of the area and the weight of coverage.Solid substances will retain the active component by occlusion and willoften have better adhesion to the foliage being treated forchemotherapeutic or herbicidal use. The solid carriers for use in solidpulverulent compositions, either as concentrates or as treatingformulations contain surfactants to prevent local high concentrations,and to facilitate distribution on the infested environment. Suitablesolid diluents are those which render the compositions permanently dryand free flowing. Thus, hygroscopic materials are to be avoided unlessthe compositions also contain a separate substance to serve as an aid tothe flowability. Effective solid diluents, preferably pulverulent orgranular in form so as to be effective carriers for the activeingredient, are the natural clays, such as china clays, the bentonitesand the atapulgites; other minerals in natural state such as talc,pyrophyllite, quartz, diatomaceous earth, fullers earth, chalk, rockphosphate and sulfur; and the chemically modified minerals, such as theacid washed bentonite, precipitated calcium phosphate, precipitatedcalcium carbonate and colloidal silica. These dil-uents may represent asubstantial portion, for example 50 to 98 percent by Weight of theentire formulation as applied to the soil or to plant surfaces.

Other adjuvants having specific activity in the control of certaininsects, fungus, bacteria, mites or objectionable plants may be added toincrease the spectrum of utility. These may be any additives known to beuseful toxicants, and especially for the control of plant and animalspecies which have a measure of resistance to the principal toxicant.

Although the invention is described with respect to the above explicitexamples, it is not intended that the details thereof are limitations onthe scope of the invention except to the extent incorporated in thefollowing claims.

3. The method of controlling insects, which comprises contacting saidorganisms with a compound of the structure wherein R is alkyl of up to12 carbon atoms.

4. The method of controlling insect population which comprisescontacting the said insect with a compound of the stnlcture structure RX H Z X v/K X1 Y i /Ex wherein the X symbols represent atoms selectedfrom the class consisting of chlorine and bromine; wherein W is an atomselected from the class consisting of oxygen and 15 sulfur; wherein R isselected from the class consisting of hydrocarbons of the classconsisting of alkyl radicals of up to 12 carbon atoms, alkenyl radicalsof up to 12 carbon atoms, alkynyl radicals having up to 12 carbon atoms,and cycloalkyl having from three to seven carbon atoms; and saidhydrocarbon radicals having substituents of the class consisting ofphenyl, alkyloxy, alkylthio, CH: 01 H 01 bromine and chlorine, the alkylmoiety of said substituents having up to four carbon atoms; wherein Z isselected from 01 l the class consisting of X and hydrogen; and wherein Yl 01 O is selected from the class consisting of R, X and hydrogen. 1 2.The method of controlling insects, which comprises contacting the saidorganisms with a compound of the 01 H 01 structure H C, i X

I C1 0 No references cited. 01

1 H JULIAN s. LEvrrr, Primary Examiner.

STANLEY J. FRIEDMAN, Assistant Examiner. wherein R is alkyl of up to 12carbon atoms.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,281,317 October 25, 1966 Victor Mark It is hereby certified that errorappears in the above numbered patent requiring correction and that thesaid Letters Patent should read as corrected below.

Column 4, lines 20 to 27, the formula should appear as shown belowinstead of as in the patent:

H c1 H (:1 H3C'CHCH3 Signed and sealed this 28th day of November 1967.

(SEAL) Attest:

EDWARD M. FLETCHER,JR. EDWARD J. BRENNER Attesting Officer Commissionerof Patents

1. THE METHOD OF CONTROLLING INSECTS, WHICH COMPRISES CONTACTING THESAID ORGANISMS WITH A COMPOUND OF THE STRUCTURE